KR20100014549A - Palladium(0)-dibenzylidene acetone complexes - Google Patents
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- dibenzylidene acetone
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 11
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000000921 elemental analysis Methods 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims 2
- 238000004458 analytical method Methods 0.000 abstract description 9
- 239000000376 reactant Substances 0.000 abstract 2
- 239000000047 product Substances 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 101150003085 Pdcl gene Proteins 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 7
- 239000001632 sodium acetate Substances 0.000 description 7
- 235000017281 sodium acetate Nutrition 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- -1 palladium (0) dibenzylidene acetone complexes Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
Description
본 발명은 팔라듐(0)-디벤질리덴 아세톤 착물 Pdx(dba)y 및 이의 제조방법에 관한 것이다. 이런 유형의 착물은 C-C 커플링 반응용으로 사용된다.The present invention relates to a palladium (0) -dibenzylidene acetone complex Pd x (dba) y and a process for its preparation. Complexes of this type are used for CC coupling reactions.
문헌[Y. Takahashi et al., Journal of the Chemical Society, Chemical Communications 1065 (1970), 및 Inorganic Synthesis, 28, 110 (1990)]에는 팔라듐(0) 착물 Pd(dba)2가 기재되어 있다. 이러한 착물은 나트륨 아세테이트(NaAc)와 과량의 dba(dba:Pd≥3)를 고온 메탄올 Na2PdCl4(Takahashi) 또는 PdCl2 용액(Inorganic Synthesis)에 첨가함으로써 제조된다. 용액을 교반하에 방랭시키면 착물이 침전된다. 이어서 착물을 여과 수집하고, 먼저 물로 세척한 다음 아세톤으로 세척한다.[Y. Takahashi et al., Journal of the Chemical Society, Chemical Communications 1065 (1970), and Inorganic Synthesis, 28, 110 (1990) describe the palladium (0) complex Pd (dba) 2 . This complex is prepared by adding sodium acetate (NaAc) and excess dba (dba: Pd ≧ 3) to hot methanol Na 2 PdCl 4 (Takahashi) or PdCl 2 solution (Inorganic Synthesis). The solution is allowed to cool under stirring to precipitate the complex. The complex is then collected by filtration, first washed with water and then with acetone.
문헌[T. Ukai et al., J. Organomet. Chem. 65, 253 (1974)]에는 Pd2(dba)3 x CHCl3로서의 팔라듐(0) 디벤질리덴 아세톤 착물의 합성이 개시되어 있다. 이를 위해, PdCl2를 dba-NaOAc와 메탄올의 고온 용액에 첨가한다. 혼합물을 40℃에서 4시간 동안 교반하면 생성물이 침전되며 이를 클로로포름에서 재결정한다. 클로로포름은 착물에 결합된 채로 잔류한다.T. Ukai et al., J. Organomet. Chem. 65, 253 (1974) discloses the synthesis of palladium (0) dibenzylidene acetone complexes as Pd 2 (dba) 3 × CHCl 3 . To this end, PdCl 2 is added to a hot solution of dba-NaOAc and methanol. The mixture is stirred at 40 ° C. for 4 hours to precipitate the product which is recrystallized from chloroform. Chloroform remains bound to the complex.
문헌[Herrmann/Brauer, Synthetic Methods of Organometallic and Inorganic Chemistry, vol. 1, 160 (1996)]에는 Pd2(dba)3 x dba의 합성이 기재되어 있으며, 전술한 바의 문헌[T. Ukai 및 Y. Takahashi]을 인용하고 있다. 이에 따라 재현된 생성물은 상당량의 불용성 분획으로 오염되어 있다.Herrmann / Brauer, Synthetic Methods of Organometallic and Inorganic Chemistry, vol. 1, 160 (1996) describes the synthesis of Pd 2 (dba) 3 × dba, see T. Ukai and Y. Takahashi. The product thus reproduced is contaminated with a significant amount of insoluble fraction.
문헌[M.C. Mazza, C.G. Pierpont, Inorg. Chem., 12, 2955 (1973)]에는 Pd(dba)3 x C6H6의 합성이 기재되어 있다.MC Mazza, CG Pierpont, Inorg. Chem., 12, 2955 (1973) describes the synthesis of Pd (dba) 3 × C 6 H 6 .
문헌[M.C. Mazza, C.G. Pierpont, J.C.S., Chem. Comm., 207 (1973)]에는 Pd2(dba)3 x CH2Cl2의 합성이 기재되어 있다.MC Mazza, CG Pierpont, JCS, Chem. Comm., 207 (1973), describes the synthesis of Pd 2 (dba) 3 × CH 2 Cl 2 .
문헌에 기재된 생성물은 완전히 특성해석이 이루어지지는 않았다. 따라서, 선행 참고문헌에는 화합물의 팔라듐 함량이나 조성 어느 쪽도 정확하게 기재되어 있지 않다. 근본적인 원인은 추측하건대 적합한 용매의 부족으로 인한 생성물의 정제 불능이다. CHC 또는 방향족 탄화수소에 용해시, 용매와의 반응에 의해 새로운 생성물이 발생한다.The products described in the literature have not been fully characterized. Therefore, the preceding references do not accurately describe either the palladium content or the composition of the compound. The underlying cause is probably the inability to purify the product due to the lack of suitable solvents. When dissolved in CHC or aromatic hydrocarbons, a new product is produced by reaction with a solvent.
문헌[M.C. Mazza and C.G. Pierpont, Inorg. Chem., 12, 2955 (1973)]에서는 Pd-dba 착물의 가역성 시리즈 - Pd 함량이 각각 23.2%, 18.5%, 및 13.1%인 Pd2(dba)3, Pd(dba)2, 및 Pd(dba)3 - 가 존재한다고 결론내리고 있다.MC Mazza and CG Pierpont, Inorg. Chem., 12, 2955 (1973), describes the reversible series of Pd-dba complexes—Pd 2 (dba) 3 , Pd (dba) 2 , and Pd (dba) having Pd contents of 23.2%, 18.5%, and 13.1%, respectively. 3 ) is concluded.
문헌[P. Espinet, A.M. Echavarren (Angew. Chem. 2004, 116, 4808)]에 따르 면, 2금속 착물로서 용어 [Pd2(dba)3]*dba가 Pd(dba)2보다 더 정확하다.P. According to Espinet, AM Echavarren (Angew. Chem. 2004, 116, 4808), the term [Pd 2 (dba) 3 ] * dba as a bimetallic complex is more accurate than Pd (dba) 2 .
Pdx(dba)y 착물의 분석에는 어려움이 따르는데, 그 이유는 불용성 성분이 원소분석 결과를 왜곡하고, Pdx(dba)y 착물의 용해로 즉시 다른 화합물이 유도되기 때문이며, 여기에서 용매는 부가 착물을 형성한다(addition-complexed).The analysis of the Pd x (dba) y complex is difficult because the insoluble component distorts the elemental analysis results and the dissolution of the Pd x (dba) y complex immediately leads to other compounds, where the solvent is added Addition-complexed.
팔라듐(0)-디벤질리덴 아세톤 착물의 대규모 생산의 경우, 순도가 높고 여과에 용이하게 투입될 수 있는 결정질 생성물을 고수율로 수득하는 것이 필수이다. 화합물의 비용-효율적인 생산을 위해서는, 건조 시간을 가능한 한 짧게 유지하는 것도 중요하다. 순도와 관련하여, 해당 화합물은 이를 예를 들면 CHC 또는 방향족 탄화수소에 용해시킬 경우 불용성 분획을 전혀 함유하지 않거나 소량만을 함유하는 것이 절대적으로 중요하다. 이러한 요건은 생성물에 존재하는 모든 Pd가 생성물의 촉매적 응용에 이용될 수 있게 보장한다. 불용성 Pd-함유 분획과, 특히, 금속 Pd는 균일 촉매 공정에 이용될 수 없다. 따라서 이러한 유형의 오염물은 바람직하지 않다.For large scale production of palladium (0) -dibenzylidene acetone complex, it is essential to obtain a high yield of crystalline product which is of high purity and can be easily introduced into filtration. For cost-effective production of the compounds, it is also important to keep the drying time as short as possible. With regard to purity, it is absolutely important that the compound contains no or only a small amount of insoluble fraction when it is dissolved in, for example, CHC or aromatic hydrocarbons. This requirement ensures that all Pd present in the product can be used for catalytic application of the product. Insoluble Pd-containing fractions and, in particular, metal Pd, cannot be used in homogeneous catalytic processes. Thus, this type of contaminant is undesirable.
본 발명의 목적은 팔라듐(0)-디벤질리덴 아세톤 착물의 순도를 증가시키고, 이를 위해 불용성 분획을 최소화하며, 특히, 염소화 탄화수소의 부가-착물 형성을 방지하는 것이다.It is an object of the present invention to increase the purity of the palladium (0) -dibenzylidene acetone complex and to minimize the insoluble fraction for this purpose, in particular to prevent the addition-complex formation of chlorinated hydrocarbons.
이러한 목적을 충족하기 위해서, 알코올 중에서 Pd-함유 유리체(遊離體), 특히 Pd 염을 디벤질리덴 아세톤 및 나트륨 아세테이트와 반응시킴으로써 불용성 분획이 적은 Pd(dba)2가 제공된다. 이를 위해, 알코올 중의 디벤질리덴 아세톤을 제공하고, 특히 용해, 및 57℃로 가열한다. 이어서 Pd-함유 유리체, 특히 Pd 염, 예를 들면 PdCl2, H2PdCl4, (NH4)2PdCl4, Na2PdCl4 또는 K2PdCl4를 가열된 용액에 용해시킨 다음 나트륨 아세테이트를 첨가한다. Pd(dba)2가 용액으로부터 침전되며 완전한 분리를 촉진하기 위해 용액을 냉각시킨다. 침전된 생성물을 여과에 투입하고, 먼저 알코올로, 이어서 석유 스피릿으로 세척한 다음, 진공하에 40℃에서 건조시킨다. 이렇게하여 매우 순수한 Pd(dba)2가 생성될 수 있다. 할로겐-함유 탄화수소, 특히 염소화 탄화수소는 착물의 생산에서 기피된다. 수득된 생성물의 팔라듐:디벤질리덴 아세톤의 몰비는 1:2±0.1 범위이다. 이렇게하여, CHC-불용성 분획에 대하여, 제공될 수 있는 팔라듐(0)-디벤질리덴 아세톤 착물의 순도는 99, 바람직하게는 99.5, 특히 99.9 wt.%이며, 지배적인 분획은 추정상 Pd(dba)2이다. 따라서, 불용성 분획은 1 wt.%, 특히 1 wt.‰ 미만으로 감소된다. 할로겐-함유 화합물, 특히 염소-함유 화합물이 기본적으로 부재한다. 또한, 착물에 방향족 용매가 포함되지 않는다. 본 발명에 따르면, 할로겐-함유 화합물이나 방향족 용매 어느 쪽도 사용되지 않는다. 순수한 출발 생성물을 사용하여, CHC 또는 방향족 탄화수소에 의한 오염을 1 wt.‰ 미만, 특히 100 ppm 미만, 바람직하게는 10 ppm 미만으로 유지하기가 용이하다.To meet this purpose, Pd (dba) 2 with low insoluble fraction is provided by reacting Pd-containing vitreous, especially Pd salt, with dibenzylidene acetone and sodium acetate in alcohol. To this end, dibenzylidene acetone in alcohol is provided, in particular dissolved, and heated to 57 ° C. Pd-containing vitreous, in particular Pd salts, for example PdCl 2 , H 2 PdCl 4 , (NH 4 ) 2 PdCl 4 , Na 2 PdCl 4 or K 2 PdCl 4 is dissolved in the heated solution and then sodium acetate is added. Pd (dba) 2 is precipitated from the solution and the solution is cooled to promote complete separation. The precipitated product is put into filtration, first washed with alcohol and then with petroleum spirit and then dried at 40 ° C. under vacuum. In this way very pure Pd (dba) 2 can be produced. Halogen-containing hydrocarbons, in particular chlorinated hydrocarbons, are avoided in the production of complexes. The molar ratio of palladium: dibenzylidene acetone of the obtained product is in the range of 1: 2 ± 0.1. In this way, for the CHC-insoluble fraction, the purity of the palladium (0) -dibenzylidene acetone complex that may be provided is 99, preferably 99.5, in particular 99.9 wt.%, And the dominant fraction is presumably Pd (dba ) 2 . Thus, the insoluble fraction is reduced to less than 1 wt.%, In particular less than 1 wt. Halogen-containing compounds, in particular chlorine-containing compounds, are basically absent. In addition, the complex does not contain an aromatic solvent. According to the invention, neither halogen-containing compounds nor aromatic solvents are used. Using pure starting products, it is easy to maintain contamination by CHC or aromatic hydrocarbons below 1 wt. ‰, in particular below 100 ppm, preferably below 10 ppm.
본 발명에 따르면, 팔라듐 함량이 19 내지 23 wt.%, 특히 20 내지 21 wt.%인 팔라듐(0)-디벤질리덴 아세톤 착물은 알코올 중의 디벤질리덴 아세톤을 반응기에 공급하여 60℃로 가열함으로써 제공된다. 이어서 여기에 Pd-함유 유리체, 특히 Pd 염, 예를 들면 H2PdCl4, (NH4)2PdCl4, K2PdCl4, Na2PdCl4, 또는 PdCl2를 용해시킨다. 나트륨 아세테이트를 첨가하고 냉각시켜 반응 생성물을 침전시킨다. 침전된 생성물을 여과에 투입하고, 먼저 알코올로, 이어서 석유 스피릿으로 세척한 다음, 진공하에 40℃에서 건조시킨다. CHC-불용성 오염물은 1 wt.% 미만을 차지한다. 높은 팔라듐 함량은 높은 비율의 Pd2(dba)3를 수반한다.According to the invention, a palladium (0) -dibenzylidene acetone complex having a palladium content of 19 to 23 wt.%, In particular 20 to 21 wt.% Is obtained by feeding dibenzylidene acetone in alcohol to the reactor and heating it to 60 ° C. Is provided. Then Pd-containing vitreous, in particular Pd salts, for example H 2 PdCl 4 , (NH 4 ) 2 PdCl 4 , K 2 PdCl 4, Na 2 PdCl 4, or PdCl 2 is dissolved. Sodium acetate is added and cooled to precipitate the reaction product. The precipitated product is put into filtration, first washed with alcohol and then with petroleum spirit and then dried at 40 ° C. under vacuum. CHC-insoluble contaminants account for less than 1 wt.%. High palladium content involves a high proportion of Pd 2 (dba) 3 .
본 발명에 따르면, 팔라듐 함량이 13 내지 17 wt.%, 특히 15 내지 16.5 wt.%인 팔라듐(0)-디벤질리덴 아세톤 착물은 Pd-함유 유리체를, 특히 클로라이드 형태로, 예를 들면 PdCl2, H2PdCl4, (NH4)2PdCl4, Na2PdCl4 또는 K2PdCl4를 첨가하기 전에 알코올 중의 디벤질리덴 아세톤을 50℃로 가열함으로써 제공된다. 나트륨 아세테이트를 가하고, 반응 혼합물을 냉각시켜 반응 생성물을 침전시킨 다음, 침전된 생성물을 여과에 투입하여, 먼저 알코올로, 이어서 석유 스피릿으로 세척한 다음, 최종적으로는 진공하에 40℃에서 건조시킨다. 오염물은 1 wt.% 미만을 차지한다. 낮은 팔라듐 함량은 높은 비율의 Pd(dba)3를 수반한다.According to the invention, palladium (0) -dibenzylidene acetone complexes having a palladium content of 13 to 17 wt.%, In particular 15 to 16.5 wt.%, Can be used to form Pd-containing vitreous, especially in chloride form, for example PdCl 2 , H 2 PdCl 4 , (NH 4 ) 2 PdCl 4 , Na 2 PdCl 4 or It is provided by heating dibenzylidene acetone in alcohol to 50 ° C. before adding K 2 PdCl 4 . Sodium acetate is added and the reaction mixture is cooled to precipitate the reaction product, after which the precipitated product is put into filtration, first washed with alcohol and then with petroleum spirit and finally dried at 40 ° C. under vacuum. Contaminants account for less than 1 wt.%. Low palladium content involves a high proportion of Pd (dba) 3 .
본 발명에 따르면, 5‰ 미만, 바람직하게는 1‰ 미만의 유기 용매 또는 CHC-불용성 Pd 분획으로 오염되는 Pdx(dba)y 착물이 제공된다. 미량의 잔류 오염물은 본질적으로 알코올과 석유 스피릿이다. Pdx(dba)y 착물인 Pd(dba)3, Pd(dba)2, 및 Pd2(dba)3가 생성되었다. 따라서 Pdx(dba)y 착물의 화학량론은 Pd(dba)3 내지 Pd2(dba)3이다.According to the present invention there is provided a Pd x (dba) y complex that is contaminated with less than 5 ‰, preferably less than 1 ‰ organic solvent or CHC-insoluble Pd fraction. Trace residual contaminants are essentially alcohol and petroleum spirits. Pd x (dba) y complexes Pd (dba) 3 , Pd (dba) 2 , and Pd 2 (dba) 3 were generated. The stoichiometry of the Pd x (dba) y complex is therefore Pd (dba) 3 to Pd 2 (dba) 3 .
비교 실시예Comparative Example
1) Inorganic Synthesis, 28, 110 (1990)에 따른 합성1) Synthesis according to Inorganic Synthesis, 28, 110 (1990)
합성은 불활성 가스하에서 수행되었다. 2.096 g(11.73 mmol)의 PdCl2 및 0.686 g(11.73 mmol)의 NaCl을 아르곤하에 공급하고, 59 mL의 메탄올을 첨가하였다.Synthesis was performed under inert gas. 2.096 g (11.73 mmol) of PdCl 2 and 0.686 g (11.73 mmol) of NaCl were fed under argon and 59 mL of methanol was added.
이어서, 반응 혼합물을 밀폐된 플라스크에서 18시간 동안 밤새 교반하였다. 이어서, 암적갈색 용액을 아르곤하에 G3 프리트를 통해 여과하였다. 프리트에는 명백히 어떠한 잔사도 존재하지 않았다.The reaction mixture was then stirred overnight for 18 hours in a closed flask. The dark red brown solution was then filtered through G3 frit under argon. There was obviously no residue in frit.
여액을 293 mL의 메탄올을 사용하여 500 mL 들이 3구 플라스크로 이송하여 60℃로 가열하였다. 이 온도에서, 8.563 g(36.54 mmol)의 디벤질리덴 아세톤을 아르곤하에 첨가하였다. 이어서, 17.595 g(214.49 mmol)의 나트륨 아세테이트를 첨가하였다.The filtrate was transferred to a 500 mL three neck flask using 293 mL of methanol and heated to 60 ° C. At this temperature, 8.563 g (36.54 mmol) of dibenzylidene acetone were added under argon. Then 17.595 g (214.49 mmol) of sodium acetate were added.
다량의 적색 고체가 침전되었다. 계속해서, 반응 혼합물을 실온으로 냉각시켰다. 생성물을 여과 제거한 다음, 300 mL의 메탄올, 300 mL의 물, 및 300 mL의 아세톤으로 세척하였다. 생성물을 진공하에 실온에서 건조시켰다.A large amount of red solid precipitated out. Subsequently, the reaction mixture was cooled to room temperature. The product was filtered off and washed with 300 mL of methanol, 300 mL of water, and 300 mL of acetone. The product was dried under vacuum at room temperature.
외관: 암갈색 고체Appearance: Dark Brown Solid
용해도 시험:Solubility Test:
1.00 g의 생성물을 150 mL의 클로로포름에 용해시킨 다음 실온에서 30분간 교반하였다. 이어서 용액을 멤브레인 필터를 통해 흡인하였다. 필터를 30 mL의 물과 30 mL의 아세톤으로 세척하고, 이어서 진공하에 45℃에서 밤새 건조시켰다. 잔사는 1.4%를 차지하였다.1.00 g of product was dissolved in 150 mL of chloroform and then stirred at room temperature for 30 minutes. The solution was then aspirated through a membrane filter. The filter was washed with 30 mL of water and 30 mL of acetone and then dried overnight at 45 ° C. under vacuum. The residue accounted for 1.4%.
결과:result:
m(생성물): 6.4 g m (product): 6.4 g
Pd에 대한 수율: 94% Yield for Pd: 94%
CHCl3-불용성 성분: 1.4%CHCl 3 -Insoluble Ingredients: 1.4%
분석:analysis:
2) Y. Takahashi 등(J. Chem. Soc. Chem. Commun. 1065 (1970))에 따른 합성2) Synthesis according to Y. Takahashi et al. (J. Chem. Soc. Chem. Commun. 1065 (1970))
합성은 불활성 가스하에서 수행되었다.Synthesis was performed under inert gas.
1.55 kg(6616 mmol)의 디벤질리덴 아세톤, 657.9 g(2208 mmol)의 Na2PdCl4, 및 56 L의 메탄올을 반응 플라스크에서 57℃로 가열하였다. 이어서, 1.47 kg(17920 mmol)의 나트륨 아세테이트를 첨가하였다. 다량의 적색 고체가 침전되었다.1.55 kg (6616 mmol) dibenzylidene acetone, 657.9 g (2208 mmol) Na 2 PdCl 4 , And 56 L of methanol were heated to 57 ° C. in a reaction flask. Then 1.47 kg (17920 mmol) sodium acetate were added. A large amount of red solid precipitated out.
계속해서, 반응 혼합물을 실온으로 방랭시켰다. 생성물을 여과 제거한 다음, 50 L의 물과 50 L의 아세톤으로 세척하였다. 생성물을 진공하에 실온에서 건조시켰다.Subsequently, the reaction mixture was allowed to cool to room temperature. The product was filtered off and washed with 50 L of water and 50 L of acetone. The product was dried under vacuum at room temperature.
외관: 암갈색 고체Appearance: Dark Brown Solid
용해도 시험:Solubility Test:
1.00 g의 생성물을 150 mL의 클로로포름에 용해시키고 실온에서 30분간 교반하였다. 용액을 멤브레인 필터를 통해 흡인하였다. 필터를 30 mL의 물과 30 mL의 아세톤으로 세척하고, 이어서 진공하에 45℃에서 밤새 건조시켰다. 잔사는 1.1%를 차지하였다.1.00 g of product was dissolved in 150 mL of chloroform and stirred at room temperature for 30 minutes. The solution was aspirated through a membrane filter. The filter was washed with 30 mL of water and 30 mL of acetone and then dried overnight at 45 ° C. under vacuum. The residue accounted for 1.1%.
결과:result:
m(생성물): 1053 gm (product): 1053 g
Pd에 대한 수율: 93%Yield for Pd: 93%
CHCl3-불용성 성분: 1.1 wt.%CHCl 3 -insoluble component: 1.1 wt.%
분석:analysis:
실험 1Experiment 1
합성은 불활성 가스하에서 수행되었다. 300 mL의 메탄올을 아르곤하에 반응 플라스크에 공급하고 57℃로 가열하였다. 이어서, 8.245 g(35.2 mmol)의 디벤질리덴 아세톤 및 3.495 g(1.248 g Pd, 11.7 mmol Pd)의 Na2[PdCl4]를 아르곤 유동의 존재하에 첨가하였다.Synthesis was performed under inert gas. 300 mL of methanol was fed to the reaction flask under argon and heated to 57 ° C. 8.245 g (35.2 mmol) of dibenzylidene acetone and 3.495 g (1.248 g Pd, 11.7 mmol Pd) of Na 2 [PdCl 4 ] were then added in the presence of argon flow.
이어서, 7.80 g(95.1 mmol)의 무수 Na-아세테이트를 57℃에서 반응 혼합물에 첨가하였다. 실온으로 냉각한 후, 교반기를 가동 중지하고, 혼합물을 1.5시간 동안 정치시켜 생성물이 침전되었다. 상등액을 경사시키고, 생성물을 300 mL의 세척 용액(메탄올/완전 탈염수 = 1/1)으로 세척하여 NaCl이 존재하지 않게 하였다. 생성물을 70 mL의 물(클로라이드 시험: 음성), 이어서 300 mL의 아세톤과 200 mL의 석유 스피릿으로 세척하였다. 생성물을 진공하에 40℃에서 밤새 건조시켰다. 7.80 g (95.1 mmol) of anhydrous Na-acetate were then added to the reaction mixture at 57 ° C. After cooling to room temperature, the stirrer was turned off and the mixture was left for 1.5 hours to precipitate the product. The supernatant was decanted and the product was washed with 300 mL of wash solution (methanol / completely demineralized water = 1/1) to eliminate the presence of NaCl. The product was washed with 70 mL of water (chloride test: negative) followed by 300 mL of acetone and 200 mL of petroleum spirit. The product was dried overnight at 40 ° C. under vacuum .
외관: 적갈색 고체Appearance: Maroon Solid
용해도 시험:Solubility Test:
1.00 g의 생성물을 150 mL의 클로로포름에 용해시킨 다음, 실온에서 30분간 교반하였다. 용액을 멤브레인 필터를 통해 흡인하였다. 필터를 30 mL의 물과 30 mL의 아세톤으로 세척하고, 이어서 필터를 진공하에 45℃에서 밤새 건조시켰다. 잔사는 0%에 달했다.1.00 g of product was dissolved in 150 mL of chloroform and then stirred at room temperature for 30 minutes. The solution was aspirated through a membrane filter. The filter was washed with 30 mL of water and 30 mL of acetone, and then the filter was dried overnight at 45 ° C. under vacuum. The residue reached 0%.
결과:result:
m(생성물): 6.4 gm (product): 6.4 g
Pd에 대한 수율: 95.4%Yield for Pd: 95.4%
CHCl3-불용성 성분: 0%CHCl 3 -Insoluble Ingredients: 0%
분석:analysis:
실험 2Experiment 2
반응이 50℃의 개시온도에서 수행되는 것을 제외하고는, 합성은 실험 1에서와 같이 수행되었다.Synthesis was carried out as in Experiment 1, except the reaction was carried out at an onset temperature of 50 ° C.
결과:result:
m(생성물): 7.05 gm (product): 7.05 g
Pd에 대한 수율: 92.4%Yield for Pd: 92.4%
CHCl3-불용성 성분: 0.2%CHCl 3 -Insoluble Ingredients: 0.2%
분석:analysis:
실험 3Experiment 3
샘플이 4배 더 큰 것을 제외하고는, 합성은 실험 1에서와 같이 수행되었다. 반응은 60℃의 개시온도에서 수행되었다.Synthesis was performed as in Experiment 1, except the sample was four times larger. The reaction was carried out at an onset temperature of 60 ° C.
결과:result:
m(생성물): 24.682 g m (product): 24.682 g
Pd에 대한 수율: 96.4%Yield for Pd: 96.4%
CHCl3-불용성 성분: 0.2%CHCl 3 -Insoluble Ingredients: 0.2%
분석:analysis:
실험 4Experiment 4
합성은 실험 3에서와 같이 수행되었다. 반응은 60℃의 개시온도에서 수행되었다.Synthesis was performed as in Experiment 3. The reaction was carried out at an onset temperature of 60 ° C.
결과:result:
m(생성물): 25.0 gm (product): 25.0 g
Pd에 대한 수율: 96.2%Yield for Pd: 96.2%
CHCl3-불용성 성분: 0%CHCl 3 -Insoluble Ingredients: 0%
분석:analysis:
실험 5Experiment 5
반응이 60℃의 개시온도에서 수행되고, 이 온도에서 5분간 유지시킨 후에만 냉각이 개시되는 것을 제외하고는, 합성은 실험 1에서와 같이 수행되었다.Synthesis was carried out as in Experiment 1, except that the reaction was carried out at an initiation temperature of 60 ° C. and cooling started only after holding at this temperature for 5 minutes.
결과:result:
m(생성물): 6.15 gm (product): 6.15 g
Pd에 대한 수율: 99.5%Yield for Pd: 99.5%
CHCl3-불용성 성분: 0.1%CHCl 3 -Insoluble Ingredients: 0.1%
분석:analysis:
Claims (11)
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| DE102007018703.5 | 2007-04-18 | ||
| PCT/EP2008/002785 WO2008128644A1 (en) | 2007-04-18 | 2008-04-09 | Palladium(0)-dibenzylidene acetone complexes |
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| CN102892707B (en) | 2010-02-16 | 2014-10-29 | 约翰逊马西有限公司 | Method for preparing Pd2(dba)3.CHCl3 |
| CN102010445B (en) * | 2010-11-30 | 2013-06-12 | 金川集团有限公司 | Preparation method of di(dibenzalacetone)palladium(0) |
| RU2645680C1 (en) * | 2016-12-28 | 2018-02-27 | Федеральное государственное унитарное предприятие "Институт химических реактивов и особо чистых химических веществ Национального исследовательского центра "Курчатовский институт" (НИЦ "Курчатовский институт"- ИРЕА) | Dichloride di(phenylacetonitrile) palladium and the method for its production |
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| US4347232A (en) * | 1981-06-17 | 1982-08-31 | Fmc Corporation | Preparation of hydrogen peroxide from its elements |
| DE10105751B4 (en) * | 2001-02-08 | 2005-09-29 | Oxeno Olefinchemie Gmbh | Process for the preparation of 1-octene |
| AU2003296175A1 (en) * | 2002-12-24 | 2004-07-22 | The Honjo Chemical Corporation | Organic platinum-group element compound of fullerenol and/or fullerenol hydrogen sulfate ester, utilization of the same, and process for producing the same |
| JP2004217626A (en) * | 2002-12-24 | 2004-08-05 | Honjo Chemical Corp | Organic platinum group element compound of fullerenol and/or fullerenol hydrogen sulfate ester, its use and method for producing the same |
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| US7999126B2 (en) | 2011-08-16 |
| RU2009142427A (en) | 2011-05-27 |
| EP2134733B1 (en) | 2013-07-17 |
| CN101663311A (en) | 2010-03-03 |
| ZA200907200B (en) | 2010-11-24 |
| JP2010524870A (en) | 2010-07-22 |
| EP2134733A1 (en) | 2009-12-23 |
| US20100167408A1 (en) | 2010-07-01 |
| BRPI0810450A8 (en) | 2015-12-01 |
| DK2134733T3 (en) | 2013-10-14 |
| KR101464015B1 (en) | 2014-11-20 |
| SA08290234B1 (en) | 2012-02-12 |
| JP5542655B2 (en) | 2014-07-09 |
| RU2470029C2 (en) | 2012-12-20 |
| BRPI0810450A2 (en) | 2014-10-14 |
| DE102007018703A1 (en) | 2008-10-23 |
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